WO2004083265A1 - エチレン系重合体及び成形体への応用 - Google Patents
エチレン系重合体及び成形体への応用 Download PDFInfo
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- WO2004083265A1 WO2004083265A1 PCT/JP2004/001689 JP2004001689W WO2004083265A1 WO 2004083265 A1 WO2004083265 A1 WO 2004083265A1 JP 2004001689 W JP2004001689 W JP 2004001689W WO 2004083265 A1 WO2004083265 A1 WO 2004083265A1
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- Prior art keywords
- ethylene
- polymerization
- molecular weight
- polymer
- measured
- Prior art date
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- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 238000000434 field desorption mass spectrometry Methods 0.000 description 1
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
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- 238000009532 heart rate measurement Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
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- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000001907 polarising light microscopy Methods 0.000 description 1
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- 230000001172 regenerating effect Effects 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
- C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Definitions
- the present invention relates to an ethylene-based polymer which provides a molded article having excellent moldability and excellent mechanical strength and appearance, and a molded article obtained therefrom.
- High-density polyethylene which is used for a wide range of applications such as films, pipes, and bottle containers, has traditionally been produced using Ziegler's Natta catalyst or chromium catalyst.
- Ziegler's Natta catalyst or chromium catalyst due to the nature of these catalysts, there was a limit in controlling the molecular weight distribution and composition distribution of the polymer.
- JP-A-11-106432 discloses a low-molecular-weight polyethylene and a high-molecular-weight ethylene / ⁇ -olefin copolymer obtained by polymerization using a supported geometrically constrained single-site catalyst (CGCZBorate-based catalyst).
- CGCZBorate-based catalyst a supported geometrically constrained single-site catalyst
- Compositions prepared by melt blending are disclosed. However, since the molecular weight distribution of the composition is not wide, the fluidity of the composition may be poor. Further, in the claims of the above publication, a preferred carbon number range of ⁇ -olefin which is copolymerized with ethylene is not disclosed, but when the carbon number is less than 6, mechanical strength may not be sufficiently exhibited. is expected.
- MwZMn molecular weight distribution
- the mechanical properties such as impact strength are not sufficient as compared with the narrow molecular weight distribution of the single-stage product.
- the expectation that the above-mentioned strength is inferior if the composition distribution of the single-stage polymerized product is broad is based on the cross-fractionation (CFC) data described in March 2001, p. This is apparent from the cross-fractionation (CFC) data shown in FIG. 2 of JP-A-11-106432.
- WO 01/25328 discloses an ethylene polymer obtained by solution polymerization using a catalyst system comprising CpTiNP (u) 3 Cl 2 and a portal or alumoxane.
- EP1201711A1 discloses that a polymer obtained by slurry polymerization in the presence of a catalyst system consisting of ethylene'bis (4,5,6,7-tetrahydro-1-indull) zirconium dichloride and methylalumoxane supported on silica.
- An ethylene polymer is disclosed.
- the single-stage polymer has a wide molecular weight distribution (MwZMn), so the molecular weight distribution of the single-stage polymer is narrow, and it is expected that the impact strength and the like are inferior to those of the single-stage polymer.
- ethylene polymers have a multimodal molecular weight distribution. If the molecular weight difference between the multimodals is large, it is difficult to mix them by melt kneading, so that multistage polymerization is usually employed. Multistage polymerization is generally performed continuously. In the case of such continuous multi-stage polymerization, the time during which the polymer stays in a polymerization vessel in a polymerization environment where low-molecular-weight substances are generated, and the time when the polymer stays in a polymerization vessel in a polymerization environment where a high-molecular-weight polymer is generated.
- Distribution usually occurs in the ratio of
- a difference in molecular weight between particles may occur.
- a difference in molecular weight was observed even when a Ziegler catalyst such as that described in Japanese Patent No. 821037 was used.
- the polymer particles were well mixed even in the pelletization by kneading.
- the polymer particles are often not sufficiently mixed by pelletization by ordinary melt-kneading because of a narrow molecular weight distribution.
- a methyl branch is present in a molecular chain because a methyl branch is by-produced during polymerization. It is known that methyl branching is incorporated into crystals and weakens the crystals (see, for example, Polymer, Vol. 31, p. 1999, 1990), which results in the mechanical degradation of ethylene (co) polymers. The strength had been reduced.
- a hard and brittle component is generated when almost no ⁇ -olefin is contained, whereas when the ⁇ -olefin is excessively copolymerized, a soft and crystal structure is formed. The formation of weak components can result in stickiness. Further, there is a problem that the low-molecular-weight substance is attached to the surface of the molded product as a powdery substance due to a wide molecular weight distribution.
- An ethylene polymer obtained by polymerization using a meta-mouth catalyst described in JP-A-9-183816 or the like has methyl branches in the molecular chain as a result of by-produced methyl branches during the polymerization. . Methyl branches are incorporated into the crystal and weaken the crystal structure. This caused the mechanical strength to decrease. Further, an ethylene polymer having a very large molecular weight has not been disclosed so far.
- Ethylene polymers obtained by polymerization using chromium catalysts had poor mechanical strength due to small molecular spread due to containing long chain branches.
- a methyl branch was present in the molecular chain due to the by-produced methyl branch during the polymerization.
- Methyl branches are incorporated into the crystal and weaken the crystal structure. This led to a decrease in mechanical strength.
- a copolymer of ethylene and ⁇ -olefin almost all ⁇ -olefin is used. If not included, hard and brittle components were formed, while excessive copolymerization of ⁇ -olefin resulted in stickiness and soft, weakly crystalline components.
- methyl branching is present in the molecular chain because methyl branching is by-produced during polymerization.
- I was Methyl branches are incorporated into the crystal and weaken the crystal structure. That caused the mechanical strength to drop.
- the molecular spread was small due to the inclusion of long-chain branching, and the mechanical strength was insufficient.
- methyl branches and long-chain branches were produced as by-products during the polymerization, so that methyl branches and long-chain branches were present in the molecular chains.
- the methyl branch is incorporated into the crystal and weakens the crystal strength. This caused the mechanical strength to decrease.
- the molecular spread was small, and the molecular weight distribution was wide, resulting in poor mechanical strength.
- the ethylene polymer obtained by low-temperature polymerization using a catalyst containing Ta and Nb complexes described in JP-A-6-233723 and the like has a weight average molecular weight (Mw) and a number average molecular weight (Mn) measured by GPC. In some cases, the moldability was not sufficient because the ratio (Mw / Mn) was small. Disclosure of the invention
- the present inventors have excellent researches on an ethylene-based polymer having excellent moldability and excellent mechanical strength.
- CFC cross fractionation
- E Ethylene polymer which satisfies at least one of the following is to give a molded article having excellent moldability, particularly excellent mechanical strength and excellent appearance, especially blow molded articles, pipes and pipe joints. And completed the present invention.
- the weight average molecular weight (Mw) of the component eluted at 73 to 76 ° C does not exceed 4,000.
- the ethylene polymer (E) according to the present invention preferably satisfies all of the following requirements (1 ′) to (7 ′) in addition to the above requirements.
- the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC is in the range of 5 to 70.
- the elution temperature of the peak of the strongest peak with a molecular weight of less than 100,000 (° 0, the elution temperature of the peak of the strongest peak with a molecular weight of 100,000 or more with ⁇ 2 (° C) , (Ti-Ta) (° C) is in the range of 0 to 11 ° C.
- this ethylene polymer may be referred to as an ethylene polymer ( ⁇ ′).
- ethylene polymer ⁇ ′
- Further preferred ethylene-based polymers according to the present invention in addition to the above requirements, the requirement that the number of methyl branches measured by 13 C-NMR is less than 0.1 per 1000 carbon atoms (in the following description, Requirements (sometimes called ' ⁇ ')).
- such an ethylene polymer may be referred to as an ethylene polymer ( ⁇ ").
- a particularly preferred ethylene polymer according to the present invention satisfies the following requirements (1 '") and (2"') simultaneously in addition to all the above requirements.
- ethylene polymer ( ⁇ "') The smoothness coefficient R obtained from the surface roughness of the extruded strand does not exceed 20 pm.
- this ethylene polymer may be referred to as an ethylene polymer ( ⁇ "').
- the ethylene-based polymer ( ⁇ ) of the present invention is applied to a blow molded article, the following requirements ( 1 ⁇ ) to (3 ⁇ ⁇ ) must be simultaneously satisfied in addition to the above-mentioned requirements to be satisfied by the ethylene-based polymer ( ⁇ ). Is preferred Les ,.
- the ethylene polymer may be referred to as an ethylene polymer (E B) there also more preferred ethylene polymer for blow molded article, the above requirements (1 B:) ⁇ (3 pressurized forte following requirement ( ⁇ ') and (2 beta' to B) at the same time satisfying it is preferably [the ethylene polymer), in the following description may be referred to as an ethylene polymer (E beta '). ], Particularly preferably preferably satisfies the following requirements (1 ⁇ '') [the ethylene polymer, in the following description may be referred to as ethylene-based polymer (E beta ").].
- the flexural modulus measured at 23 ° C according to ASTM-D-790 is in the range of 1,500 to 1,800 MPa.
- the ethylene polymer (E) satisfies the requirements (1) to (7). It is preferable that the ethylene polymer ( ⁇ ') satisfy the above requirement (1 "). More preferably, the ethylene polymer ( ⁇ ′′) is particularly preferably an ethylene polymer ( ⁇ ′′ ′) that also satisfies the requirements (1 ′ ′′) and (2 ′′ ′).
- IP ethylene polymer
- 2 ⁇ the following requirements
- (IF) Contains 0.10 to: 1.00 mol% of a structural unit derived from ⁇ -olefin having 6 to 10 carbon atoms.
- (2P) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC is in the range of 11 to 70.
- this ethylene-based polymer may be referred to as an ethylene-based polymer ( ⁇ ′).
- ethylene polymer for pipes the requirement (lp) and in addition to the following requirements ( ⁇ ') and (2 [rho' be satisfied) simultaneously preferred [the ethylene polymer, the following In the description, an ethylene polymer (sometimes referred to as ⁇ ⁇ ').
- Equation (Eq-2) is satisfied.
- the ethylene polymer (E) is an ethylene polymer ( ⁇ ') which also satisfies the requirements (1) to (7). More preferably, the ethylene polymer ( ⁇ ') is an ethylene polymer ( ⁇ ") that also satisfies the above requirement (1"). ") Is particularly preferably an ethylene-based polymer ( ⁇ '") which also satisfies the above requirements (1'") and (2 '"). It can be molded into molded articles, inflation molded articles, cast molded articles, extruded lamination molded articles, extruded molded articles such as pipes and irregular shapes, foam molded articles, injection molded articles, etc.
- molded articles may have a portion made of an ethylene polymer and a portion made of another resin.
- the ethylene-based polymer may be a product obtained by crosslinking the ethylene-based polymer in the molding process. Among them, when used for blow-molded articles and extruded articles such as pipes and deformed shapes, excellent properties are provided. BRIEF DESCRIPTION OF THE FIGURES
- FIG. 1 is a CFC contour map of the ethylene-based polymer obtained in Example 1.
- Figure 2 is a T 2 a three-dimensional GPC Chiya over preparative viewed from the low temperature side of the ethylene polymer obtained in Example 1 (bird's eye view).
- FIG. 3 is a three-dimensional GFC chart (bird's eye view) of the ethylene-based polymer obtained in Example 1 as viewed from a high temperature side.
- FIG. 4 is a GPC curve of an elution component of the ethylene polymer obtained in Example 1 at a peak temperature [(T 2 ⁇ 1) to T 2 ] (° C.).
- FIG. 5 is a GPC curve of a component of the ethylene polymer obtained in Example 1 which elutes at 73 to 76 (° C.).
- FIG. 6 is a GPC spring of a component of the ethylene polymer obtained in Example 1 which elutes at 95 to 96 (° C.).
- FIG. 7 is a CFC contour map of the ethylene-based polymer obtained in Comparative Example 1.
- FIG. 9 shows a three-dimensional GPC chart (bird's eye view) and Ti of the ethylene-based polymer obtained in Comparative Example 1 as viewed from the high temperature side.
- FIG. 10 is a GPC curve of an elution component of the ethylene polymer obtained in Comparative Example 1 at a peak temperature [(T 2 ⁇ 1) to T 2 ] (° C.).
- FIG. 11 is a GPC curve of a component of the ethylene polymer obtained in Comparative Example 1, which elutes at 73 to 76 (° C.).
- FIG. 12 shows the components of the ethylene polymer obtained in Comparative Example 1 which eluted at 95 to 96 (° C.).
- FIG. 13 is a graph showing the elution curve of components of the ethylene polymer obtained in Comparative Example 1 eluting at 0 to 145 (° C.) and the integrated value of the component amounts.
- FIG. 14 is a CFC contour map of the ethylene polymer obtained in Comparative Example 5.
- FIG. 15 shows a three-dimensional GPC chart (bird's eye view) and T2 of the ethylene-based polymer obtained in Comparative Example 5, as viewed from the low-temperature side.
- FIG. 16 shows a three-dimensional GPC chart of the ethylene polymer obtained in Comparative Example 5 as viewed from the high temperature side. And a bird's-eye view.
- FIG. 17 is a GPC curve of an elution component of the ethylene-based polymer obtained in Comparative Example 5 at a peak temperature [(T 2 -1) to T 2 ] (° C.).
- FIG. 18 is a GPC curve of a component of the ethylene polymer obtained in Comparative Example 5, which elutes at 73 to 76 (° C.).
- FIG. 19 is a GPC curve of a component of the ethylene polymer obtained in Comparative Example 5, which elutes at 95 to 96 (° C.).
- FIG. 20 is a CFC contour map of the ethylene polymer obtained in Example 3.
- FIG. 21 shows a three-dimensional GPC chart (bird's eye view) and ⁇ 2 of the ethylene-based polymer obtained in Example 3 as viewed from the low temperature side.
- FIG. 22 is a three-dimensional GPC chart (bird's eye view) and ⁇ of the ethylene-based polymer obtained in Example 3 as viewed from the high temperature side.
- FIG. 23 is a GPC curve of an elution component of the ethylene polymer obtained in Example 3 at a peak temperature [(T 2 ⁇ 1) to T 2 ] (° C.).
- FIG. 24 is a GPC curve of a component of the ethylene polymer obtained in Example 3 which elutes at 73 to 76 (° C.).
- FIG. 25 is a GPC curve of a component of the ethylene polymer obtained in Example 3, which elutes at 95 to 96 (° C.).
- FIG. 26 is a graph showing the elution curve of the component of the ethylene polymer obtained in Example 3 which elutes at 0 to 145 (° C.) and the integrated value of the component amount.
- FIG. 28 is a GPC chart showing an example of GPC separation analysis.
- FIG. 29 shows an example of a measurement result (75 times) of a crystal structure of an ethylene-based polymer.
- FIG. 30 shows an example of a measurement result (150 times) of a crystal structure of an ethylene-based polymer.
- FIG. 31 is a schematic view of a pinch-off section.
- FIG. 32 shows a specimen for a 23 ° C. bow I tension fatigue test.
- FIG. 33 is a diagram showing a comparison of the results of the 80 ° C. tensile fatigue test between the example and the comparative example.
- FIG. 34 is a diagram showing a comparison of the results of a 23 ° C. tensile fatigue test between the example and the comparative example.
- FIG. 35 is a diagram in which the results of a 23 ° C. tensile fatigue test of the example and the comparative example are plotted against the density of the sample.
- the ethylene polymer (E) according to the present invention is an ethylene polymer containing 0.01 to 1.20 mol% of a structural unit derived from ⁇ -olefin having 6 to 10 carbon atoms, and is usually a homopolymer of ethylene. And a copolymer of ethylene and ⁇ -olefin having 6 to 10 carbon atoms.
- ⁇ -olefins having 6 to 10 carbon atoms for example, 1-hexene, 4-methyl-1-pentene, 3- Methyl-1-pentene, 1-octene, 1-decene and the like can be mentioned.
- ⁇ -olefins it is preferable to use at least one selected from 1-hexene, 4-methyl-1-pentene and 1-octeneca.
- the ethylene polymer ( ⁇ ) according to the present invention is characterized by satisfying either of the following requirements (1) or (2) in cross fractionation (CFC).
- the weight average molecular weight (Mw) of the component eluted at 73 to 76 ° C does not exceed 4,000.
- the weight-average molecular weight (Mw) measured by GPC of the component eluted at 73 to 76 ° C. in the cross fractionation (CFC) does not exceed 4,000. If more concrete terms, the weight average molecular weight of about GPC peak molecular weight is detected at 108 following areas (Mw) Les exceed 4,000.
- the preferred range of the weight average molecular weight (Mw) is 2,000 to 4,000, more preferably 2,500 to 3,500.
- Such an ethylene polymer has a low content of a high molecular weight component in which ⁇ -olefin is copolymerized, or does not contain a component having a relatively low molecular weight and a short chain branch, In that case, it has excellent long-term physical properties such as fatigue strength as a compact.
- the ethylene- ⁇ -olefin copolymer described in JP-A-11-106432 does not satisfy the range because of its wide composition distribution, and the ethylene-based polymer described in WO01 / 25328 has a relatively small molecular weight even for components having a relatively small molecular weight. This range is not satisfied due to the presence of short-chain branching due to copolymerization of ⁇ -olefin.
- Ethylene polymers such as conventional Ziegler catalysts and chromium catalysts, do not satisfy the range because of their wide composition distribution.
- An ethylene polymer falling within this range can be produced by using a catalyst system as described below and setting polymerization conditions as described below. More specifically, when polymerized under the conditions described in Example 3 of the present application, the weight-average molecular weight (Mw) of the component eluted at 73-76 ° C in the temperature-elution fractionation using a cross fractionation (CFC) device Is 2,900, and unless the catalyst and polymerization temperature are changed, and unless ⁇ -olefin is supplied to the first polymerization reactor, ⁇ -olefin is further supplied to the second polymerization reactor.In this case, 900 g of 1-hexene is supplied. Unless it exceeds hr, the weight average molecular weight (Mw) will be less than 4,000.
- CFC cross fractionation
- the ethylene-based polymer (E) according to the present invention has a cross-fractionated CFC in which the total area of all peaks based on the components eluted at 70 to 85 ° C is Sx, and the components eluted at 0 to 145 ° C. If the total area of all the peaks based on the total area is S total , the relationship represented by the following equation (Eq-1) is satisfied.
- Such an ethylene polymer that satisfies Requirement (2) has a low content of the same high molecular weight component as ⁇ -olefin as described in Requirement (1), or has a relatively low molecular weight. And that it does not contain components that have short-chain branching, Excellent long-term physical properties such as fatigue strength.
- the ethylene- ⁇ - ⁇ -olefin copolymer described in JP-A-11-106432 does not satisfy the relationship of the above formula (Eq-1) due to a wide composition distribution
- the ethylene-based copolymer described in WO01 / 25328 Does not satisfy the relationship of the above formula (Eq-1) because even a component having a relatively small molecular weight has short-chain branching due to copolymerization of ⁇ -olefin.
- Conventional ethylene polymers, such as Ziegler catalysts and chromium catalysts also have a wide composition distribution, and therefore do not satisfy the relationship of the above formula (Eq-1).
- S x and S tota i in the above equation (Eq-1) are values based on infrared analysis of the stretching vibration of the CH bond
- the value of S x / S tota i is 70 to Equivalent to the weight percentage of components eluting at 85 ° C to components eluting at 0-145 ° C.
- all components are eluted by scanning in the region of 0 to 145 ° C, so that S x / S t .
- the value of ta i can be translated into the weight% of the amount of the eluted component at 70 to 85 ° C. based on the unit weight of the ethylene polymer.
- an ethylene-based polymer in this range can be produced.
- the left side of the above formula (Eq-1), ie, (S x / S tota i) was obtained in the cross fractionation (CFC) of the obtained ethylene-based polymer.
- a more preferred form of the ethylene polymer (E) is an ethylene copolymer ( ⁇ ') satisfying the following requirements (1 to (7')).
- the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC is in the range of 5-70.
- the ethylene polymer ( ⁇ ′) according to the present invention usually contains 0.02 to: 1.00 mol% of a structural unit derived from ⁇ -olefin having 6 to 10 carbon atoms.
- the structural unit derived from ethylene is usually 99-99.98 mol%, preferably I 99.5-99.98 mol%, more preferably 99.6-99.98 mol%, ⁇ -olefin power, the derived repeating unit is usually 0.02-1 mol%, preferably 0.02-mol%.
- the ethylene polymer ( ⁇ ') may contain an ethylene homopolymer, in which case the structural unit derived from ethylene in the ethylene / ⁇ -olefin copolymer portion is usually 95 to 99.%. , mol%, preferably 97.5-99.% mol%, more preferably 98-99.96 mol%, and the repeating unit derived from ⁇ -olefin is 0.04-5 mol%, preferably 0.04-2.5 mol% , More preferably in a proportion of 0.04 to 2.0 mol%.
- the repeating unit derived from ⁇ -olefins in the total polymer is usually 0.02 to 1 mol%, preferably 0.02 to 0.5 mol%, more preferably 0.02 to 1 mol%. ⁇ 0.4 mol%.
- the number of carbon atoms of ⁇ -olefin is 5 or less, the probability that ⁇ -olefin is incorporated into the crystal becomes high (see Polymer, Vol. 31, 1999, 1990), and as a result, the strength becomes weak. . If the number of carbon atoms in the ⁇ -olefin exceeds 10, the activation energy of the flow increases, and the change in viscosity during molding is undesirably large.
- the side chain (branch caused by ⁇ -olefin which is copolymerized with ethylene) may be crystallized, and the amorphous part is weakened. Absent.
- the density (d) of the ethylene-based polymer () ′) according to the present invention is 945 to 970 kg Zm 3 , preferably 947 to 9 kg / m 3 , more preferably 950 to 9 kg / m in 135 ° C decalin.
- Limit measured The viscosity ([ ⁇ ]) is in the range of 1.6-4.0 dl / g, preferably 1.7-3.8 dl / g, more preferably 1.8-3.7 dl / g.
- Ethylene polymers having a density and intrinsic viscosity in these ranges are excellent in balance between hardness and moldability.
- the value within the above numerical range can be obtained. Can be increased or decreased.
- the ethylene polymer ( ⁇ ′) according to the present invention has an Mw / Mn (Mw: weight average molecular weight, ⁇ : number average molecular weight) of usually 5 to 70, preferably, measured by gel permeation chromatography (GPC). It is in the range of 5-50.
- Mw weight average molecular weight
- ⁇ number average molecular weight
- GPC gel permeation chromatography
- Mw / Mn can be increased by increasing the molecular weight difference between the components.
- a polymer having Mw / Mn in the above range has an excellent balance between mechanical strength and moldability. Specifically, when polymerized under the conditions described in Example 3 of the present application, Mw / Mn becomes 14.8.
- the ethylene supplied to the first polymerization tank is changed from 5.0 kg / hr to 7.0 kg / hr and the hydrogen is changed from 57 N-liter / lr to 125 N-liter / hr, the ethylene polymer generated in the first polymerization tank is changed.
- MwZMn Due to the decrease in molecular weight, MwZMn is reduced to about 18, while ethylene supplied to the second polymerization tank is reduced from 4.0 kg / hr to 3.3 kg / hr, hydrogen is reduced from 0.2 N-liter Zhr to 0.07 N-liter Zhr. If this is changed, the molecular weight of the ethylene polymer generated in the second polymerization tank will increase, and Mw / Mn will be about 22.
- the hydrogen supplied to the first polymerization tank is 52 N-liter / hr
- the ethylene supplied to the second polymerization tank is 6.0 kg / hr
- the hydrogen is 0.45 N-liter Zhr
- the 1-hexene is 200 g / hr
- Mw / Mn is about 12.
- the elution temperature at the peak of the strongest peak having a molecular weight of less than 100,000 is Ti (° C), and the molecular weight is 100,000 or more
- the elution temperature of the strongest peak apex in the case of the T 2 (° C), in the range one T 2) (° C) is 0 to 11 ° C, preferably 0 ° C In the range, more preferably in the range of 0-9 ° C.
- an ethylene-based polymer within this range can be produced by using a catalyst system described below and setting polymerization conditions as described below.
- the peak at the top of the strongest peak having a molecular weight of 100,000 or more was obtained. Child size is in the range of 200,000-800,000.
- the fraction eluted at T 2 (° C.) refers to the component eluted at [(T 2 — :!) to T 2 ] (.C).
- Such an ethylene-based polymer is excellent in balance between long-term physical properties such as fatigue properties and moldability.
- An ethylene polymer in this range can be produced by using a catalyst system as described below and setting polymerization conditions as described below.
- the GPC curve of the fraction eluted at T 2 has the highest molecular weight. High peak crest The molecular weight of the point can be increased or decreased in a specific range.
- CFC cross fractionation
- the molecular weight at the peak of the strongest peak does not exceed 28,000. Usually: 15,000 to 27,000.
- Such an ethylene-based polymer has a low molecular weight and does not contain a component having a short-chain branch, and in that case, is excellent in long-term physical properties such as fatigue strength.
- An ethylene polymer falling within this range can be produced by using a catalyst system as described below and setting polymerization conditions as described below. Specifically, when the polymerization was performed under the conditions described in Example 3, the strongest peak in the GPC curve of the component eluted at 95% to 95 ° C in the temperature-elution fractionation using a cross fractionation (CFC) device The molecular weight at the top of is 22,000, and unless the catalyst and polymerization temperature are changed, and unless ⁇ -olefin is supplied to the first polymerization reactor, the amount of hydrogen supplied to the second double reactor is more than 10 N-liter / hr. Unless otherwise stated, the Mw falls within this range.
- ethylene-based polymer (F) a more preferred form is a methyl compound measured by isC-NMR.
- Such a polymer has a strong crystal structure and therefore excellent mechanical strength. Since the ethylene-based polymer produced using the catalyst system as exemplified in (1) is below the detection limit (0.03 per 1000 carbon atoms), no methyl branch is detected.
- ethylene-based polymers E "
- a particularly preferred embodiment is an ethylene-based copolymer ( ⁇ " ') which satisfies the following requirements (1' ") to (2 '") simultaneously.
- the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight ( ⁇ ) of each curve is in the range of 1.5-3.5.
- the weight average molecular weight (MW2) of the curve separated on the high molecular weight side is in the range of 200,000 to 800,000.
- the weight-average molecular weight (Mw 2 ) of the curve separated on the high molecular weight side was It is in the range of '200,000-800,000.
- Mw 2 the weight average molecular weight of the curve separated on the high molecular weight side
- the ethylene supplied to the second polymerization tank is 6.0 kg / hr
- the hydrogen is 0.35 N-liter Zhr
- the 1-hexene is 200 g / hr
- the Mw 2 is 312,000
- the ethylene supplied to the second polymerization tank is 3.0
- kg / hr hydrogen is 0.07 N-liter Zhr
- 1-hexene supplied to the second polymerization tank is 30 g / hr
- Mw 2 is 539,000.
- An ethylene polymer having Mw 2 in this range has an excellent balance between strength and moldability.
- the smoothness coefficient R obtained from the surface roughness of the extruded strand does not exceed 20 ⁇ , preferably does not exceed 15 ⁇ .
- the smoothness coefficient R determined from measurements does not exceed 20 ⁇ , preferably does not exceed 15 ⁇ .
- the size of the ethylene polymer particles produced by the gas phase polymerization or slurry polymerization is about several + P m ⁇ 2mm, the shape history of the polymer particles Remaining
- R is larger than 20 ⁇
- the surface of the extrudate becomes rougher and the R becomes larger than 20 ⁇ .
- an ethylene-based polymer in which R does not exceed 20 ⁇ usually does not exceed 15 ⁇
- R does not exceed 20 ⁇
- fluctuations in the range of 0 to 20 ⁇ may occur at places unrelated to the essence of foreign matters during film formation, scratches on dies, measurement errors, etc. Therefore, R exceeds 20 ⁇ .
- the ethylene polymer having a value of R exceeding 20 ⁇ is obtained, for example, by subjecting the ethylene polymer powder obtained in Example 3 to Labo Plastomill manufactured by Toyo Seiki Co., Ltd. If melt kneading is performed for a very long time, such as at 190 ° C, 25 rpm, and 15 minutes using a screw kneader, it is possible to obtain an ethylene polymer having an R of less than 20 pm. by doing It is possible to make R smaller, but it may be accompanied by a structural change due to decomposition or cross-linking.
- Example 1 of the present application when two-stage polymerization is carried out in a batch system, R does not exceed 20 pm even without long-time melt-kneading. Further, of the ethylene polymers obtained in Example 3, an ethylene homopolymer was extracted from the first polymerization vessel and separately melted with an ethylene polymer obtained by single-stage slurry polymerization under the conditions of the second polymerization vessel. Even by kneading, an ethylene polymer having an R not exceeding 20 m may be obtained.
- the ethylene-based polymers (E), (E '), (E ") and ( ⁇ "') according to the present invention are melted at 190 ° C. and cooled at 20 ° C. to form a 0.5 mm thick press sheet microtome.
- the section is characterized by the fact that a continuous crystal structure exceeding ⁇ is not observed when the section is observed with a polarizing microscope.
- a microtome section of a 0.5 mm thick pressed sheet melted at 190 ° C and cooled at 20 ° C was observed with a polarizing microscope, a continuous crystal structure exceeding ⁇ was observed.
- Such an ethylene-based polymer is excellent in mechanical strength.
- the ethylene-based polymer powder obtained in Example 3 of the present application was melted for a long period of time at 190 ° C., 25 rpm, 10 minutes or more using a Labo Plastomill (batch type bidirectional rotary twin-screw kneader) manufactured by Toyo Seiki Co., Ltd. If kneaded, an ethylene polymer can be obtained without a continuous crystal structure exceeding ⁇ being observed.
- Example 1 when two-stage polymerization was carried out in a batch system, an ethylene polymer in which a continuous crystal structure exceeding ⁇ was not observed only by melt-kneading for a very short time. Can be obtained.
- an ethylene homopolymer was extracted from the first polymerization vessel, and was separately melt-kneaded with an ethylene polymer obtained by single-stage slurry polymerization under the conditions of the second polymerization vessel. In this case, a continuous crystal structure exceeding ⁇ is observed even if the kneading time is increased.
- the polymerization for obtaining the ethylene-based polymers ( ⁇ ) to ( ⁇ ′′ ′) of the present invention is preferably carried out in a slurry phase or a gas phase.
- Polymerization is preferable because two types of ethylene-based polymers having significantly different molecular weights in the primary particle order (nanometer order) corresponding to one active point of the catalyst are mixed during polymerization.
- Ethylene polymer which is preferably used in the blow molded article (E B)
- E beta is a structural unit concentration derived from ⁇ - Orefin carbon atoms 6 to 10, Mw / Mn value Contact Yopi cross- fractionation in (CFC) ( ⁇ _ ⁇ 2) values are each less (1 beta) Preferably, it is limited as in (2) and (3B).
- the derived structural unit is contained in an amount of 0.02 to 0.20 mol%.
- ethylene polymer which is preferably used in the blow molded article (E B) typically includes 0.02 ⁇ 0.2Mol% constitutional units derived from ⁇ - Orefin 6 to 10 carbon atoms.
- This onset Ming ethylene polymer (E B) is ethylene alone When the polymer contains no, if that is, copolymers of ⁇ - Orefuin of ethylene and having 6 to 10 carbon atoms alone, the electrically ethylene It is preferable that the constituent unit is usually present at a ratio of 99.80 to 99.98 mol%, and the repeating unit derived from ⁇ -olefin is usually present at a ratio of 0.02 to 0.20 mol%.
- the ethylene-based polymer (E B) is to contain the ethylene homopolymer, constituent units derived from ethylene in the case the ethylene ⁇ alpha-O les fin copolymer portion thereof is usually from 99.00 to 99 % mol%, repeating units derived from ⁇ -olefins are preferably present at a ratio of 0.04 to 1.00 mol%. Even when an ethylene homopolymer is contained, the repeating unit derived from the ⁇ -olefin force in the total polymer is usually 0.02 to 0.20 mol%.
- the ethylene polymer (E B ) according to the present invention which is preferably used for a molded article, has the strongest molecular weight of less than 100,000 in temperature-elution fractionation using a cross fractionation (CFC) device. If re) elution temperature for the apex of the peak, a molecular weight of 100,000 or more, the elution temperature of the strongest peak apex of the T 2 (° C), ( Ti one T 2) (° C) is 0 to 5 ° C, preferably in the range of 0-4 ° C, more preferably in the range of 0-3 ° C.
- the peak of the strongest peak means the point (ie, the shoulder) where the differential value is the closest to the mouth (ie, the shoulder) if the differential value is zero (that is, the peak of the mountain).
- Such an ethylene-based polymer has high rigidity and excellent environmental stress rupture resistance.
- An ethylene polymer in this range can be produced by using a catalyst system as described below and setting polymerization conditions as described below. ( ⁇ — ⁇ 2 ) can be increased or decreased within this range by increasing or decreasing the copolymerization amount of ⁇ -olefin.
- Ethylene polymer according to the present invention (E B), the above requirements (1 B) ⁇ preferably satisfies the following requirements (1B) and (2 beta ') in addition to (3 B) [this ethylene polymer ethylenic polymer to a (sometimes referred to as E beta], more preferably following requirement (1 beta "meet) [this ethylene polymer, the following description ethylene polymer (E beta”) In some cases.]
- the flexural modulus measured at 23 ° C according to ASTM-D-790 is in the range of 1,500 to 1,800 MPa.
- the ethylene polymer ( ⁇ ′) according to the present invention has a flexural modulus measured at 23 ° C. in the range of 1,500 to 1,800 MPa, and has an environmental stress rupture resistance ESCR (hr) at 50 ° C. of 10%. Over time Non-destructive, preferably non-broken in 50 hours or more. Flexural modulus and ESCR within this range Ethylene polymers are hard and strong, so molded products can be made thinner than before.
- the molecular weight and the polymerization ratio of each component are controlled by changing the supply ratio of hydrogen and ethylene- ⁇ -olefin to the polymerization reactor.
- an ethylene polymer having [ ⁇ ] in this range can be produced.
- the flexural modulus was 1,650 MPa
- ESCR became non-destructive in 600 hours
- 1-hexene supplied to the second polymerization tank was changed from 50 g / hr to 30 g / hr, and ethylene supplied to the second polymerization tank was changed.
- the flexural modulus When the flow rate was reduced from 4.0 kg / hr to 3.0 kg / hr, the flexural modulus was 1,780 MPa, the ESCR was 233 hours, and it became 50% broken, and the 1-hexene supplied to the second polymerization tank was 50 g / hour. When changing from hr to 65gZhr, the flexural modulus becomes 1,520MPa and ESCR becomes non-destructive in 600 hours.
- the ethylene polymer ( ⁇ ⁇ ′) according to the present invention has a tan ⁇ (loss elastic modulus G ′′ / storage elasticity) at 190 ° C. and an angular frequency of 100 md / sec measured using a dynamic viscoelasticity apparatus.
- Ratio G ′) is preferably 0.7 to 0.9 tan ⁇ force S Within this range, the pinch fusion property at the time of blow molding is excellent, and the molecular weight of the low molecular weight ethylene polymer is increased.
- tan ⁇ tends to increase.
- Pinch fusing property refers to the fusion of a cylindrical molten resin extruded from an extruder with a mold. This indicates that the resin rises and adheres well to the welded part during welding. The larger the tan ⁇ , the stronger the viscosity. In this case, it is considered that the resin easily rises.
- the ethylene polymers ( ⁇ ⁇ ), ( ⁇ ⁇ ') and ( ⁇ ⁇ ") for the blow-molded article according to the present invention are preferably soluble in decane at 140 ° C. It means that the process is not performed, and if the cross-linking process is not performed, it can be re-melted and reused, and the process of manufacturing a molded article is more simple and preferable.
- the ethylene polymer (E) satisfies the requirements () to ( 7 ') described above.
- the ethylene polymer () that preferably satisfies the above requirement () is more preferably an ethylene polymer ( ⁇ ) that satisfies the above-mentioned requirement ().
- ( ⁇ ") meets the above requirements and (2 '") It is particularly preferable that the ethylene polymer ( ⁇ ") satisfy the above-mentioned requirements.
- the ethylene polymer ( ⁇ ") is the above-mentioned requirement. (1 ⁇ '), (2 ⁇ ' is most preferably used to satisfy both) and ( ⁇ ').
- Ethylene polymer suitable for pipe applications ( ⁇ ⁇ ⁇ ⁇ ⁇ )
- the ethylene polymers ( ⁇ ), preferably ( ⁇ , more preferably ( ⁇ ′′)), and particularly preferably ( ⁇ ′′ ′) according to the present invention are ethylene polymers suitably used for pipe applications are It is preferable that the constituent unit concentration and the Mw / Mn value derived from ⁇ -olefins having 6 to 10 carbon atoms are limited to the following (lp) and (2 P ), respectively. In the following description, the obtained ethylene polymer may be referred to as an ethylene polymer (EP).
- the ethylene-based polymer (E P ) suitably used for the pipe according to the present invention generally contains 0.10 to: 1.00 mol% of a structural unit derived from ⁇ -olefin having 6 to 10 carbon atoms.
- a structural unit derived from ⁇ -olefin having 6 to 10 carbon atoms When the ethylene polymer (E P ) of the present invention does not contain an ethylene homopolymer, that is, when it is only a copolymer of ethylene and ⁇ -olefin having 6 to 10 carbon atoms, ethylene is used.
- the derived structural unit is usually present at a ratio of 99.00 to 99.90 mol%, and the repeating unit derived from ⁇ -olefin is preferably present at a ratio of usually 010 to: 1.00 mol%.
- the ethylene polymer (EP) may contain an ethylene homopolymer, in which case the structural unit derived from ethylene in the ethylene / ⁇ -olefin copolymer portion is usually 95.00 to 99.80 mol%.
- the repeating units derived from a-olefins are present in a proportion of 0.20-5.00 mol%. Even when an ethylene homopolymer is contained, the repeating unit derived from a-olefin in the total polymer is usually 0.10 to: LOO mol%.
- the ethylene polymer (EP) according to the present invention has an Mw / Mn (Mw: weight average molecular weight, Mn: number average molecule) measured by gel permeation chromatography (GPC). Amount) is usually in the range of 11 to 70, preferably 11 to 50.
- Mw weight average molecular weight
- Mn number average molecule
- Amount is usually in the range of 11 to 70, preferably 11 to 50.
- an ethylene-based polymer within this range can be produced by controlling the molecular weight and the polymerization amount ratio of each component. For example, if the difference in molecular weight of each component is increased, Mw / Mn increases.
- a polymer having Mw / Mn in the above range has an excellent balance between mechanical strength and moldability.
- Mw / Mn when polymerized under the conditions described in Example 1 using hexane as the solvent, Mw / Mn becomes 14.8.
- the weight of ethylene produced in the first polymerization tank Mw / Mn is about 18 due to the lower molecular weight of coalescing
- ethylene supplied to the second polymerization tank is 4.0 kg / hr to 3.3 kg / hr and hydrogen is 0.2 N-liter / hr to 0.07 N-liter
- MwZMn will be about 22 because the molecular weight of the ethylene polymer generated in the second polymerization tank will increase.
- hydrogen 52N- liters supplied to the first polymerization vessel and the second polymerization vessel in ethylene supplies S.OkgZhr hydrogen 0.45N- rate t torr / hr, When 200gZhr hexene to 1-, Mw / Mn Is about 12.
- the ethylene polymer (EP) of the present invention preferably satisfies the following requirements ( ⁇ ′) and (2 ⁇ ′) in addition to the above requirements (lp) and (2 P ).
- ethylene-based polymer (3 ⁇ 4) Sometimes referred to as ethylene-based polymer (3 ⁇ 4)].
- the ethylene polymer ( ⁇ ⁇ ') according to the present invention has an actual stress of 13 MPa to 17 MPa when the number of times of breakage is 10,000 times in the tensile fatigue property measured at 80 ° C with a notch in the sample, preferably 13 MPa to 17 MPa. Is 14 MPa to 16 MPa, and the actual stress when the number of times of fracture is 100,000 is in the range of 12 MPa to 17 MPa, preferably 13 MPa to 16 MPa. Notch the sample and measure at 80 ° C An ethylene polymer having a tensile fatigue strength within the above range is excellent in long-term life characteristics in which the fracture mode is brittle.
- the molecular weight of each component, the amount of ⁇ -olefin that is copolymerized with ethylene, the composition distribution, the polymerization amount ratio, and the compatibility are determined. By controlling, an ethylene polymer in this range can be produced.
- the fatigue strength can be made higher within the scope of the claims by selecting the polymerization conditions such that the composition distribution is narrowed within the range of the olefin content of 01 to 5.0 mol%. Specifically, when polymerization was performed under the conditions described in Example 3 using hexane as the solvent and granulation was performed under the conditions described in Example 3, the number of times of breakage in the tensile fatigue properties measured at 80 ° C was reduced.
- the actual stress force at 10,000 times is Sl3.7MPa, and the actual stress at 100,000 times of fracture is 13.1MPa.
- 230 ° C setting 100 rpm, full flight screw, discharge rate 50g_min, at 80 ° C
- the actual stress when the number of times of fracture is 10,000 times is 12.3 MPa
- the actual stress when the number of times of fracture is 100,000 times is 11.3 MPa, which does not satisfy the claims. This is presumed to be due to poor compatibility of the polymer particles.
- ethylene supplied to the second polymerization tank was 3.3 kg / hr
- hydrogen was 0.07 N-liter / hr
- granulation was performed under the conditions described in Example 3.
- the actual stress when the number of failures reaches 10,000 is 13.9 MPa
- the actual stress when the number of failures reaches 100,000 is 13.4 MPa.
- the polymerization conditions as in Comparative Example 1 were employed, the actual stress when the number of times of breakage was 10,000 times was 12.1 MPa in the tensile fatigue characteristics measured at 80 ° C, and the number of times of breakage was 100,000 times.
- the actual stress at that time was 11.2 MPa, which did not satisfy the claims.
- the tensile fatigue strength measured at 80 ° C for a notched sample does not appear because the amorphous phase becomes weaker.
- the absence of a continuous crystal structure exceeding ⁇ means that a microtome section of a 0.5 mm thick press sheet melted at 190 ° C and cooled at 20 ° C is observed with a polarizing microscope.
- the ethylene polymer was melted at 190 ° C using a hydraulic press molding machine manufactured by Shindo Metal Industry Co., Ltd. Form a 0.5mm thick press sheet with a cooling press set at 20 ° C, then cut using a microtome etc.
- FIGS. 29 and 30 show examples where the crystal structure is observed only in a part of the visual field and no continuous crystal structure exceeding ⁇ exists, and where the crystal structure is observed over the entire visual field. An example of a case where a continuous crystal structure exceeding ⁇ is present will be described.
- the scale bar is 0.5 mm in total length.
- Figure 29 is a photograph observed at about 75 times
- Figure 30 is a photograph observed at about 150 times.
- the actual stress (S) (MPa) of the ethylene polymer ( ⁇ ⁇ ') according to the present invention when the number of times of failure was 10,000 times in the tensile fatigue properties measured at 23 ° C without notching the sample
- the force is in the range of 19.4 to 27.2 MPa, preferably 19.6 to 27.2 MPa, or the ethylene polymer (E) according to the present invention breaks due to tensile fatigue properties measured at 23 ° C without notching the sample.
- K S (0.60d- 550.00) (Eq-3) Increased density, i.e., hardened, notched, notched, measured at 23 ° C
- the properties may be improved. If the density is changed, the mechanical properties may change if the density is changed. Therefore, this relational expression means that, despite the same density (hardness), the tensile fatigue characteristics measured at 23 ° C without notching the sample are better than before.
- the basis of the formula that defines the lower limit of S (MPa) is based on the relationship between the tensile fatigue properties and the density measured at 23 ° C without notching for the ethylene polymer obtained by the conventional technique, and the present invention.
- the relationship between the tensile fatigue properties measured at 23 ° C and the density measured at 23 ° C without the notch obtained in the above was plotted, and this was obtained to distinguish between the two, and is shown in Fig. 35.
- the basis of the equation that specifies the upper limit of S (MPa) is based on the plot of the relationship between tensile fatigue properties and density measured at 23 ° C without notching obtained in the present invention, and the area where actual measured values exist. It is an equation obtained to distinguish between a region having no higher measured value and a region having a higher value, and is shown in FIG. 35.
- the molecular weight of each component, the amount of ⁇ -olefins copolymerized with ethylene, the composition distribution, the polymerization amount ratio, and the compatibility are determined.
- an ethylene-based polymer in this range can be produced.
- using a specific single-site catalyst increasing [ ⁇ ] within the scope of the claims, selecting ⁇ -olefins having 6 to 10 carbon atoms as ⁇ -olefins to be copolymerized, and selecting ⁇ -olefins in the copolymer By reducing the amount in the range of 0 :!
- the ethylene polymers (E P ), ( ⁇ ⁇ ′) and (E P “) for pipes according to the present invention are preferably soluble in 140 ° C. decane. It means that it is not applied, and if it is not subjected to a cross-linking step, it can be re-melted and reused, and the production process of a molded article is simpler and preferable.
- the ethylene polymer (E) satisfies the above requirements (1') to (a).
- the ethylene-based polymer () ′ which is preferably an union (E F )
- the polymer ( ⁇ ") is an ethylene polymer ( ⁇ "') that also satisfies the requirements (1'") and (2 '").
- the polymer for pipes of the present invention Echile
- the emissions-based polymer, the production method of the ethylene-based polymer (E "') is the requirement ( ⁇ ') and (2 ⁇ ') those that meet together are most preferably used.
- the ethylene polymer according to the present invention includes, for example,
- ethylene is homopolymerized, or ethylene and carbon atoms
- the transition metal compound (A) is a compound represented by the following general formulas (1) and (2).
- R 7 , R 8 , R 9, R 1, Rll, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19 and R 2 Q are a hydrogen atom, Selected from a hydrocarbon group and a silicon-containing hydrocarbon group, which may be the same or different, and adjacent substituents from R 7 to R 18 may be bonded to each other to form a ring, and A is partially A divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond and Z or an aromatic ring, forms a ring structure with Y, and A includes a ring formed with Y Y may be carbon or silicon, M may be a metal selected from Group 4 of the Periodic Table, and Q may be a halogen, a hydrocarbon group, or an aryl group.
- the same or different combinations may be selected from neutral ligands capable of coordinating with on ligands or lone electron pairs.
- J is an integer of 1 to 4.
- R 7 -Rio are hydrogen, Y is carbon, M is Zr, and j is 2.
- the transition metal compound (A) used in Examples of the present application described later is specifically a force S represented by the following formula (3) and (4), and in the present invention, the transition metal compound is not limited to this transition metal compound. is not.
- the structures of the transition metal compounds represented by the above formulas (3) and (4) were determined using 270 MHz iH-NMR (JEOL GSH-270) and FD-mass spectrometry (JEOL SX-102A).
- (B-1) organometallic compound used as necessary in the present invention include organometallic compounds of Groups 1 and 2 and Groups 12 and 13 of the periodic table as described below.
- the aluminum compound used in Examples described later is triisobutylaluminum or triethylaluminum.
- the (B-2) organoaluminoxy compound used as required in the present invention may be a conventionally known aluminoxane, or may be a benzene-insoluble compound as exemplified in JP-A-2-78687. It may be an organic aluminum oxy compound.
- the compound (B- 3 ) which reacts with the crosslinked meta-mouth compound (A) of the present invention to form an ion pair (hereinafter referred to as “ionidion ionic compound”) is described in JP-A-1-501950. , JP Hei 1 Patent No. -502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US-5321106, etc. And ionic compounds, borane compounds and carborane compounds. Further, heteropoly compounds and isopoly compounds can also be mentioned. Such ionized ionic compounds (B-3) are used alone or in combination of two or more. As the component (B) used in the examples of the present invention described later, the two components (B-1) and (B-2) shown above this time are used.
- the (C) particulate carrier used as necessary in the present invention is an inorganic or organic compound, and is a granular or particulate solid.
- the inorganic compound is preferably a porous oxide, an inorganic halide, clay, a clay mineral or an ion-exchange layered compound.
- Such a porous oxide has different properties depending on the kind and the production method.
- the carrier preferably used in the present invention has a particle size of 1 to 300 ⁇ , preferably 3 to 200 pm, and a specific surface area of 50 to 1000 m. 2 / g, preferably in the range of 100 to 800 m 2 Zg, and the pore volume in the range of 0.3 to 3.0 cm 3 / g.
- Such a carrier is used by calcining at 80 to: 1000 ° C, preferably at 100 to 800 ° C, if necessary.
- the carrier used in the examples of the present application described below has an average particle diameter of 12 pm, a specific surface area of 800 m 2 Zg, and a pore volume of 1.0 cm 3 / g, manufactured by Asahi Glass Co., Ltd., unless otherwise specified. ⁇ 2 was used.
- the catalyst for polymerization of olefins comprises the crosslinked meta-mouth compound of the present invention (A), (B-1) an organometallic compound, (B-2) an organoaluminoxy compound, and (B-3) an ionized ion.
- a specific organic compound component (D) as described later can be contained, if necessary, together with at least one compound (B) selected from the acidic compounds and, if necessary, the fine particle carrier (C).
- the organic compound component (D) is used, if necessary, for the purpose of improving the polymerization performance and the physical properties of the produced polymer.
- organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, sulfonates, and the like.
- the ethylene polymer according to the present invention can be prepared by using the above-mentioned catalyst for polymerization of olefin. As described above, it can be obtained by homopolymerizing ethylene or copolymerizing ethylene with ⁇ -olefin having 6 to 10 carbon atoms.
- each component (B) may be the same or different.
- each component (B) may be the same or different.
- each component (B) may be the same or different.
- each component (B) may be the same or different.
- each component (B) may be the same or different, and may be different.
- at least two or more of the respective catalyst components may have been brought into contact in advance.
- olefin may be prepolymerized.
- the prepolymerized solid catalyst component is usually constituted by prepolymerizing polyolefin at a ratio of 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g per lg of the solid catalyst component.
- an antistatic agent, an anti-filing agent and the like may be used together or may be carried on a carrier.
- the polymerization can be carried out by any of a liquid phase polymerization method such as a solution polymerization and a suspension polymerization or a gas phase polymerization method.
- a liquid phase polymerization method such as a solution polymerization and a suspension polymerization or a gas phase polymerization method.
- the suspension polymerization and the gas phase polymerization method are preferably employed.
- the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane and cyclohexane.
- Alicyclic hydrocarbons such as xane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof. Olefin itself can be used as a solvent.
- Component (B-1), which is used as necessary, has a molar ratio of component (B-1) to the transition metal atom (M) in component (A) [(B-1) / M] force of usually 0.01 ⁇ : Used in an amount such that it is 100,000, preferably 0.05 to 50,000.
- the component (B-2) used as necessary is a molar ratio of the aluminum atom in the component (B-2) to the transition metal atom (M) in the component (A) [(B-2) ZM] Is usually used in an amount of 10 to 500,000, preferably 20 to 100,000.
- Component (B-3) which is used as necessary, has a molar ratio [(B-3) / M] between component (B-3) and transition metal atom (M) in component (A). It is used in an amount of 1 to 100, preferably 2 to 80.
- the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1 to 0.1.
- Component (B) is added in an amount such that In the case of (B-2), component (B) is added to component (B-B) in such an amount that the molar ratio [(D) / (B-2)] is usually 0.001 to 2, preferably 0.005 to 1.
- the polymerization temperature using such a catalyst for polymerization of olefins is usually in the range of -50 to 10,250 ° C, preferably 0 to 200 ° C, particularly preferably 60 to 170 ° C.
- the polymerization pressure is usually from normal pressure to 100 kgZcm 2 , preferably from normal pressure to 50 kgZcm 2 , and the polymerization reaction may be carried out by any of batch (batch), semi-continuous and continuous methods. Can be.
- the polymerization is usually performed in a gas phase or a slurry phase in which polymer particles are precipitated in a solvent. Furthermore, polymerization is carried out in two or more stages under different reaction conditions. Among these, it is preferable to carry out by a batch method.
- the polymerization temperature is preferably from 60 to 90 ° C, more preferably from 65 to 85 ° C.
- an ethylene polymer having a narrower composition distribution can be obtained.
- the obtained polymer is in the form of particles having a size of about several to several thousand ⁇ .
- an ethylene homopolymer having an intrinsic viscosity of 0.3 to 1.8 dl / g is produced in a preceding step, and an intrinsic viscosity of 3.0 to 10.0 dl is produced in a later step.
- a method of separating the polymer from the solvent and unreacted ⁇ -olefin by a solvent separation device For example, simultaneously or as quickly as possible withdrawing the contents of the polymerization tank from the polymerization tank, (1) a method of separating the polymer from the solvent and unreacted ⁇ -olefin by a solvent separation device; A method of forcibly discharging the solvent and unreacted ⁇ -olefin into the system by adding an inert gas, and 3 controlling the pressure applied to the contents to forcibly remove the solvent and unreacted ⁇ -olefin from the system.
- a polymerization catalyst such as methanol
- examples thereof include a method of adding a substance, and a method of cooling the content to a temperature at which polymerization is not considered to substantially occur. These methods may be performed alone or in combination.
- the molecular weight of the resulting ethylene-based polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can be adjusted by the difference of the component (B) used.
- the polymer particles obtained by the polymerization reaction may be pelletized by the following method.
- a suitable good solvent for example, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene, and xylene. Then, the solvent is removed, followed by mechanical blending using an extruder, a kneader or the like, and cutting to a predetermined size.
- a suitable good solvent for example, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene, and xylene.
- the ethylene-based polymer according to the present invention includes a weather-resistant stabilizer, a heat-resistant stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an anti-fogging agent, a lubricant, a dye within a range not to impair the object of the present invention.
- Additives such as nucleating agents, plasticizers, antioxidants, hydrochloric acid absorbents, antioxidants, and carbon black, titanium oxide, titanium yellow, phthalocyanine, isoindolinone, quinacridone compounds, condensed azo compounds, ultramarine, cobalt A pigment such as blue may be blended if necessary.
- the ethylene-based polymer according to the present invention can be molded into blow molded articles, inflation molded articles, cast molded articles, extruded lamination molded articles, extruded molded articles such as pipes and irregular shapes, foam molded articles, injection molded articles, and the like. . Further, it can be used for fibers, monofilaments, nonwoven fabrics and the like. These molded articles include molded articles (laminates and the like) including a portion composed of an ethylene-based polymer and a portion composed of another resin.
- the ethylene polymer may be one crosslinked in the molding process. It is preferable to use the ethylene-based polymer according to the present invention in an extruded product such as a blow-molded product, a pipe, or a deformed shape, because excellent properties are provided.
- the ethylene polymer (EB) for a blow molded article according to the present invention can be formed into a bottle container, an industrial chemical can, a gasoline tank, or the like by blow molding. These shaped bodies, a portion consisting of E styrene-based polymer (E B), the molded body comprising a portion consisting of another resin (laminated body, and the like). Also, if the ethylene polymer (E B) contains a pigment, the concentration is usually 0.01 -3.00 wt%.
- the ethylene polymer (E P ) for a pipe according to the present invention can be molded into a pipe or a pipe joint formed by injection molding.
- These molded articles include molded articles (laminates and the like) including a portion made of an ethylene (co) polymer and a portion made of another resin.
- the ethylene-based polymer if (E B) contains a pigment, the concentration is usually from 0.01 to 3.00 by weight%. Measurement methods for various physical properties
- 0.1 parts by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and n-octadecyl-3 as a heat stabilizer are added to 100 parts by weight of the particulate ethylene polymer.
- 0.1 part by weight of-(4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate and 0.05 part by weight of calcium stearate as a hydrochloric acid absorbent are added.
- Methyl content ⁇ per 1,000 carbon in the molecular chain of the ethylene polymer was measured by 1 3 C-NMR. The measurement was performed using a Lambda 500 type nuclear magnetic resonance apparatus ⁇ ⁇ : 500 MHz manufactured by JEOL Ltd. The number of integration was measured at 10,000 to 30,000 times. The main chain methylene peak (29.97 ppm) was used as a chemical shift standard. Diameter 10mm commercial NMR measurement quartz glass tube, the sample 250 ⁇ 400mg and Wako Pure Chemical Industries Co., Ltd. special grade o- dichlorobenzene: ISOTEC Co.
- benzene - d 6 5: mixture of 1 (volume ratio) 2 ml of the solution was added, heated at 120 ° C., and the solution dispersed uniformly was subjected to NMR measurement. Assignment of each absorption in the solid R spectrum was carried out according to the Chemical Sciences No. 141 NMR—Review and Experimental Guide [1], pp. 132-133.
- the composition of the ethylene- ⁇ -olefin copolymer is usually 250 ⁇ in a sample tube of lOmmcp.
- the measurement was performed as follows using a CFC T-150A model manufactured by Mitsubishi Yuka Corporation.
- the separation column was three Shodex AT-806MS, the eluent was o-dichlorobenzene, the sample concentration was 0.1 to 0.3 wt / vol%, the injection volume was 0.5 ml, and the flow rate was 1.0 ml / min. It is.
- the sample was heated at 145 ° (: for 2 hours, then cooled to 0 ° C at 10 ° C / hr, and further held at 0 ° C for 60 minutes to coat the sample.
- the pipe capacity is 0.06 ml and the detector is a FOXBORO infrared spectrometer MIRAN 1A CVF type (CaF 2 cell).
- the absorbance mode is set to 3.42 / im (2924 cm- Infrared light of i) was detected.
- the elution temperature was divided into 35-55 fractions from 0 ° C to 145 ° C, and fractions in 1 ° C increments especially near the elution peak.
- the fraction eluted at 90 ° C refers to the component eluted at 89 ° C to 90 ° C.
- the molecular weight of the component that was not coated even at 0 ° C and the fraction eluted at each temperature was determined.
- the SEC temperature was 145 ° C
- the internal standard injection volume was 0.5 ml
- the injection position was 3.
- the data sampling time is 0.50 sec. If too many components elute in a narrow temperature range and pressure abnormalities occur, the sample concentration may be less than 0.1 wt / vol%.
- the data processing was performed with the analysis program “CFC data processing (version 1.50)” attached to the instrument.
- the cross-separation (CFC) itself can be performed with high analytical accuracy if the measurement conditions are exactly the same. It is more preferable to take several averages of force measurement, which is said to be an analytical method that reproduces the results, and take the average.
- the measurement was performed as follows using GPC-150C manufactured by Waters.
- the separation columns were TSKgel GMH6-HT and TSKgel GMH6-HTL, the column size was 7.5 mm in inner diameter and 600 mm in length, the column temperature was 140 ° C, and the mobile phase was o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.).
- Industrial and BHT Takeda Pharmaceutical 0.025% by weight as an antioxidant, moving at 1.0ml / min, sample concentration 0.1% by weight, sample injection volume 500 ⁇ 1, and differential refractometer as detector. Using.
- Standard polystyrene has a molecular weight of Mw ⁇ 1,000 and Mw> 4xl0 using one company made Toso for 6, l, using a pressure chemi-Cal, Inc. for 000 ⁇ Mw ⁇ 4xl0 6.
- the molecular weight calculation is a value obtained by universal calibration and conversion to polyethylene.
- a program was created using Microsoft's EXCEL® 97 Visual 'Basic'.
- the two curves to be separated were log-normal distributions, and the molecular weight distribution curves were separated into two curves with different molecular weights by convergence calculation. Compare the recombined curve of the two separated curves with the molecular weight curve measured by GPC, and perform the calculation while changing the initial values so that the two almost match. The calculation is performed by dividing Log (molecular weight) into 0.02 intervals.
- the intensity was normalized so that the area of the actually measured molecular weight curve and the area of the recombined curve of the two separated curves were 1, and the measured intensity (height) at each molecular weight and the intensity of the recombined curve were normalized.
- the calculation of separating the curve is repeated until the peak becomes 0.2 or less, preferably 0.1 or less.
- the difference between Mw / Mn of the peak separated on the low molecular weight side and Mw / Mn of the peak separated on the high molecular weight side is set to 1.5 or less.
- An example of the calculation is shown in FIG.
- the resin is extruded at a resin temperature of 200 ° C and a speed of 50 mm / min (3.6 cm 3 / min) using a capillary flow property tester, Capillograph 1B manufactured by Toyo Seiki Co., Ltd.
- the surface roughness is measured using the outside of the thus obtained strand or tube as a measurement surface.
- Rz is the difference between the average of the peaks from the highest peak to the fifth peak and the average of the peaks from the deepest to the fifth valley with respect to the average line with a measurement length of 10 mm. The measurement was performed three times at different locations, and the average Is the dispersion coefficient R.
- the standard deviation is calculated for Rz measured three times. If the value of standard deviation is larger than 1/2 of the value of R, which is the average value of Rz measured three times, repeat the measurement.
- R exceeds 20 ⁇ , the polymer particles are not sufficiently mixed, so that even when a thick molded body such as a pipe or a blow bottle is molded, poor flow occurs and the surface skin is reduced. Smooth force or stress concentration occurs between polymer particles, resulting in insufficient mechanical strength.
- R is 20 ⁇ or less, it can be said that no history of polymerized particles remains.
- the ethylene-based polymer is melted at 190 ° C using a hydraulic press molding machine manufactured by Shinto Metal Industry Co., Ltd., then formed into a sheet at a pressure of lOMPa, and a 0.5 mm thick press sheet is formed with a cooling press set at 20 ° C. It was created. Then, using a microtome or the like, cut to a thickness of about 0.5 mm (press sheet thickness) xlO 2020 ⁇ After that, a small amount of glycerin was applied to the cut piece, adhered tightly to the preparation, and a cover glass was placed on it to obtain an observation sample. The sample was set between cross-cold polarizing plates and observed with an optical microscope magnified to about 75 times and about 150 times. Fig.
- Fig. 30 show examples where the crystal structure is observed only in a part of the field of view and there is no continuous crystal structure exceeding ⁇ , and the crystal structure is observed in the entire field of view. In this case, a continuous crystal structure exceeding ⁇ is assumed to exist.
- the scale bar is 0.5mm in total length.
- the number of methyl branches per 10,000 carbons in the polyethylene molecular chain was measured by 13C-NMR. The measurement was performed using an EPC500 type nuclear magnetic resonance apparatus (iH; 500 MHz) manufactured by JEOL Ltd. The number of integration was measured at 10,000 to 30,000 times. The peak of main chain methylene (29.97 ppm) was used as a standard for chemical shift.
- the number of methyl branches per 1,000 carbons was calculated from the integrated intensity ratio of the absorption (19.9 ppm) of methyl groups derived from methyl branches to the integrated sum of absorptions appearing in the range of 5 to 45 ⁇ . 0.08 methyl branches per 1,000 carbon atoms If the number is less than the limit, it is not detected below the measurement limit.
- Test temperature 50 ° C Constant temperature water bath, controllable to 500 ⁇ 0.5 ° C
- Holding of sample Set in a special holder with a special bending jig in a holder of 11.75mm in length and 165mm in length.
- Nonylphenylpolyoxyethylene ethanol (commercially available under the trade name Antarox CO-630) is diluted with water and used at a 10% concentration.
- test piece of 12.7 mm width and 63.5 mm length was punched out from the 80x80x2 mm thick press sheet for ESCR property measurement described above, according to ASTM-D-790, test temperature 23 ° C, bending speed 5.0 mm / min, / 'bending It was measured at a span distance of 32.0 mm.
- tan ⁇ Details of tan ⁇ are described, for example, in Polymer Publishing Association, “Lecture 'Rheology I”, edited by The Japan Rheology Association, pages 20 to 23.
- the measurement was performed using a rheometer RDS-II manufactured by Rheometrics, and the angular frequency ( ⁇ (rad / sec)) dispersion of the storage elastic modulus G '(Pa) and the loss elastic modulus G "(Pa) was measured.
- the thickness of the sample was about 2 mm using a parallel plate with a diameter of 25 mm, the measurement temperature was 190 ° C, and G 'and G "were measured in the range of 0.0 ⁇ ⁇ ⁇ 400.
- the measurement points were 5 points per ⁇ -digit.
- the amount of strain was appropriately selected within a range of 2 to 25% so that the torque in the measurement range could be detected and the torque was not exceeded.
- blow molding was performed under the conditions of a mold closing speed of 1.4 seconds, a mold closing pressure of 5.5 t, and a blowing air pressure of 5 kg / cm 2 to obtain a cylindrical bottle having an inner capacity of l, 000 cc and a basis weight of 50 g.
- the thickness at the center of the bottle is a and the thickness at the thickest part is b.
- the thickness ratio of the pinch portion is expressed by (a / b). The larger this value is, the better the pinch shape is (see Fig. 31).
- Tensile fatigue strength (test piece shape) conforms to JIS K-6774 using a Shimadzu Servo Pulser EHF-ER1KN X4-40L. (All-round notch type, notch depth 1mm)
- the outline of the evaluation conditions is as follows; test specimen shape (56x6x60mm square notch included), test waveform and test frequency (square wave 0.5Hz), test temperature (80 ° C) ), Actual stress was measured at several points in the range of 10 18 MPa, and the number of vibrations when the sample was broken was defined as the fatigue strength. Measure at least three points with different actual stresses, measure at least three digits in the number of breaks or at least 3 MPa in the actual stress, and create an approximation formula using the log-square least-squares method. And the actual stress equivalent to 100,000 times.
- a dumbbell (ASTM-D-1822 Type S) with a thickness of 3 as shown in Fig. 32 was molded at a pressure of 100 kg / cm2 using a hydraulic heat press manufactured by Shindo Metal Industry Co., Ltd. form Jo: 240X240x3mm the thick plate create a form of ASTM-D-1822 Type S) , with another Shinto Metal Industries, Ltd. hydraulic hot press machine set at 20 ° C, and Compressing at a pressure of LOOkgZcm 2 Then, the sample taken out from the spacer was used as an evaluation sample for actual measurement.
- the 23 ° C tensile fatigue strength was measured according to JIS -7118 using a support pulser EHF-FG10KN-4LA manufactured by Shimadzu Corporation.
- Test waveform and test frequency sine wave 4Hz
- the minimum load of the load cell was 4.9 N (0.5 kgf) constant, and the maximum load was corrected by the cross-sectional area of the central part of the test specimen before the actual stress was in the range of 17 to 25 MPa.
- Several points were measured under the conditions (test temperature, test waveform and test frequency). When the sample elongated by 50% was regarded as failure, the number of vibrations at this time was taken as the fatigue strength at the actual stress of the maximum load. Measure in the range of 1 digit or more in the number of breaks or in the range of IMPa or more in the actual stress, create an approximation formula using the log-square least-squares method, and find the actual stress equivalent to 10,000 breaks.
- the obtained supported catalyst was re-slurried in 100 ml of n-decane to obtain a solid catalyst suspension.
- the catalyst component ( ⁇ ) was obtained.
- a mixed gas of ethylene and hydrogen was added so as to keep the pressure at 8.0 kgZcm 2 G, and the polymerization was carried out for 63 minutes. After the polymerization, the pressure was released and the atmosphere was replaced with nitrogen to remove an ethylene-hydrogen mixed gas.
- Example 2 The same secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles. Then, using Toyo Seiki Labo Plastmill, melt-kneading at the same set temperature, resin charge amount, number of revolutions, and melting time as used in Example 1, then take out and form a sheet with a cooling press at 20 ° C. This was cut into a suitable size to obtain a sample for measurement. Further, physical properties were measured by preparing a press sheet using the sample. The results are shown in Tables 1-3 and Table 6. According to observation with a polarizing microscope, there is no continuous crystal structure exceeding ⁇ . It can be seen that this sample has a higher tensile fatigue strength at 80 ° C than the sample used in the comparative example (see Fig. 33).
- the content was continuously supplied to the second polymerization tank together with hexane 20 litter / hr, ethylene 4.0 kgZhr, hydrogen 0.2 N-liter / hr, 1-hexene 450 gZhr, and the polymerization temperature was 70 ° C. Polymerization was continued under the conditions of a reaction pressure of 7 kgZcm 2 G and an average residence time of 1.5 hours.
- the contents of the polymerization tank are continuously withdrawn so that the liquid level in the polymerization tank becomes constant, hexane and unreacted monomers in the contents are removed by a solvent separation device, dried, and dried. Got.
- the supply of methanol to the contents as in Example 3 described later was not performed.
- FIG. 7 shows the contours of CFC fractionation
- Fig. 8 shows the three-dimensional chart (bird's eye view) viewed from the low temperature side
- Fig. 9 shows the three-dimensional chart (bird's eye view) viewed from the high temperature side.
- Figure 10 shows the GPC curve of the eluting component at (° C)
- Figure 11 shows the GPC curve of the component eluting at 73-76 (° C).
- the GPC curve is shown in FIG. Fig. 13 shows the bird's eye view (Fig. 8 or Fig. 9), where Log (M) is the X axis, Temp (° C) is the y axis, and the vertical axis is the z axis.
- the projection of the components on the yz plane (elution curve) and the integrated value of the amount of the eluted components (100 area% in total) are shown.
- the tensile fatigue strength at 80 ° C of this sample is not so high.
- the pellets of HIZEX 7700M manufactured by Mitsui Chemicals, Inc. were used as measurement samples.
- the comonomer is 1-butene.
- a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-3 and 6-8.
- a continuous crystal structure exceeding ⁇ ⁇ ⁇ did not exist in a polarizing microscope observation with a 100-fold visual field. As shown in FIG. 33, it can be seen that this sample had lower fatigue strength than the example in the 80 ° C tensile fatigue measurement. Also shown in Fig. 34 As described above, even in the 23 ° C tensile fatigue measurement, the strength is lower than those of the other examples.
- Example 1 The catalyst used in Example 1 described in JP-A-2002-53615 is used.
- C slurry by polymerization An ethylene'butene-1 copolymer having a butene-1 content of 1.7 mol% was obtained. These were mixed at a ratio of 49/51 (weight ratio), dissolved in paraxylene at 130 ° C at a concentration of lOg lOOOOml, stirred for 3 hours, and then over 1 hour to precipitate in 3000 ml of acetone at 20 ° C.
- the mixture was filtered, filtered, vacuum-dried at 60 ° C all day and night, and then melt-kneaded using a Labo Plastomill to obtain a sample for measurement. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 and 6.
- Fig. 14 shows the contours obtained by CFC separation
- Fig. 15 shows the three-dimensional chart (bird's eye view) viewed from the low temperature side
- Fig. 16 shows the three-dimensional chart (bird's eye view) viewed from the high temperature side. 2 )
- the GPC curve of the component eluted at (° C) is shown in Fig. 17, the GPC curve of the component eluted at 73-76 (° C) is shown in Fig.
- FIG. 18 the GPC curve of the component eluted at 95-96 (° C) is shown in Fig. 18.
- the GPC curve is shown in FIG.
- a T 1 T 2.
- FIG. 33 it can be seen that in the 80 ° C tensile fatigue measurement test of this sample, the fatigue strength is lower than that of the example. Further, as shown in FIG. 34, the strength was lower in the 23 ° C tensile fatigue measurement than in the other examples.
- Unreacted ethylene and hydrogen were substantially removed from the contents continuously withdrawn from the first polymerization tank by a flash drum maintained at an internal pressure of 0.2 kg Zcm 2 G and 65 ° C. Thereafter, the content was continuously supplied to the second polymerization tank together with 35 liters of hexane, 4.0 kg / hr of ethylene, 0.2 N-liter / hr of hydrogen, and 130 g / hr of 1-hexene, and the polymerization temperature was increased. Polymerization was continued under the conditions of 80 ° C., a reaction pressure of 4.5 kg Zcm 2 G, and an average residence time of 1.2 hours.
- the contents of the polymerization tank were continuously extracted so that the liquid level in the polymerization tank was constant.
- methanol was supplied at 2 L / hr to the contents extracted from the second polymerization tank to deactivate the polymerization catalyst.
- hexane and unreacted monomers in the contents were removed by a solvent separator and dried to obtain a polymer.
- Example 2 the same secondary antioxidant, heat-resistant stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles. After squeezing, the mixture was granulated using a Bravo twin screw extruder BT-30 at the same conditions of the same set temperature, resin extrusion rate, and rotation speed as in Comparative Example 2 to obtain a measurement sample. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables:! -3 and Tables 6-8.
- FIG. 20 shows the contour lines for CFC separation.
- the 3D chart (bird's eye view) viewed from the low temperature side is shown in Fig. 21
- the 3D chart (bird's eye view) viewed from the high temperature side is shown in Fig. 22, and the peak temperature (T 2 )
- Figure 23 shows the GPC curve of the eluting component at (° C)
- Figure 24 shows the GPC curve of the component eluting at 73-76 (° C).
- the curve is shown in FIG. Fig. 26 shows the yz plane of the eluted components in the bird's eye view (Fig. 21 or Fig.
- FIG. 22 when Log (M) is the X axis, Temp (° C) is the y axis, and the vertical axis is the z axis.
- the figure shows the elution curve (elution curve) and the integrated value of the eluted components (100 area% as a whole).
- FIG. 27 shows only the integrated value of the amount of the eluted component (100 area% as a whole).
- the ethylene polymers obtained (or used) in Comparative Examples 1, 3 and 5 and Examples 12 and 13 described later are also shown.
- Example 3 Observation with a polarizing microscope of the ethylene-based polymer obtained in Example 3 does not show a continuous crystal structure exceeding ⁇ .
- FIG. 33 in the 80 ° C. tensile fatigue measurement test of this sample, it can be seen that the fatigue strength is higher than the polymer used in the comparative example. Also, as shown in Fig. 34, the strength was higher in the 23 ° C tensile fatigue measurement than in the other comparative examples.
- Unreacted ethylene and hydrogen are substantially removed from the contents continuously withdrawn from the first polymerization tank by a flash drum maintained at an internal pressure of 0.2 kg / cm2G and 65 ° C.
- the content was continuously supplied to the second polymerization tank together with hexane 35 L Zhr, ethylene 3.0 kg Zhr, hydrogen 0.07 N-liter / hr, 1-hexene 30 g / hr, and the polymerization temperature was 80 ° C.
- the polymerization was continued under the conditions of a reaction pressure of 4.5 kgZcm 2 G and an average residence time of 0.8 hr.
- the contents of the polymerization tank were continuously extracted so that the liquid level in the polymerization tank was constant.
- methanol was supplied at 2 L / hr to the contents extracted from the second polymerization tank to deactivate the polymerization catalyst.
- hexane and unreacted monomers in the contents were removed by a solvent separation device and dried to obtain a polymer.
- Example 2 the same secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles. Then, using a Toyo Seiki Labo Plastomill, melt-kneading at the same set temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, then take out a cooling press at 20 ° C. Then, the sheet was cut into an appropriate size to obtain a measurement sample. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. In a polarizing microscope observation, there is no continuous crystal structure exceeding ⁇ .
- the supernatant was removed by decantation, and washing was performed four times with 50 ml of n -pentane.
- the resulting supported catalyst was reslurried in 50 ml of n -pentane to form a catalyst suspension, and the solid catalyst was suspended.
- the component ( ⁇ ) was obtained.
- This autoclave was charged with 0.25 ml (0.25 mmol) of triisobutylaluminum having a concentration of lmol liter and 20.0 ml of 1-octene, and was pressurized to 8.0 kg / cm 2 G with ethylene / hydrogen mixed gas containing 0.021 vol% of hydrogen and 65 ° C.
- the polymerization was started again at C.
- a mixed gas of ethylene and hydrogen was added so as to maintain 8.0 kg / cm 2 G, and the polymerization was performed for 19.5 minutes.
- the pressure was released, and the catalyst was deactivated by adding methanol.
- Example 2 The same secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles. After a while, using a laboplast mill manufactured by Toyo Seiki Co., Ltd., melt kneading at the same set temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, then take out and cool with a cooling press set at 20 ° C. Sheets were cut into appropriate sizes and used as measurement samples. Further, a press sheet was prepared using the sample, and physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. In a polarizing microscope observation, there is no continuous crystal structure exceeding ⁇ .
- the contents of the polymerization tank were continuously extracted so that the liquid level in the polymerization tank was constant.
- methanol was supplied at 2 L / m to the contents extracted from the second polymerization tank to deactivate the polymerization catalyst.
- hexane and unreacted monomers in the contents were removed by a solvent separator and dried to obtain a polymer.
- the solid catalyst component ( ⁇ ) obtained in Synthesis Example 2 was converted to Zr atoms at 0.13 mmol / hr, and triethyl aluminum was added at 20 mmol / hr ⁇ ethylene at 5.0 kg / hr. hr and 55N-liter / hr continuously, and while continuously extracting the contents of the polymerization tank so that the liquid level in the polymerization tank is constant, the polymerization temperature is 85 ° C and the reaction pressure is 8.1. The polymerization was carried out under the conditions of kg / cm 2 G and an average residence time of 2.6 hours.
- Unreacted ethylene and hydrogen are substantially removed from the contents continuously withdrawn from the first polymerization tank by a flash drum maintained at an internal pressure of 0.35 kg / cm2G and 60 ° C.
- the content was continuously supplied to the second polymerization tank together with 35 liters of hexane, 3.0 kg / hr of ethylene, 0.5 N-liter of Zr and 130 g / hr of 1-hexene. Polymerization was continued under the conditions of ° C, a reaction pressure of 3.9 kg / cm 2 G, and an average residence time of 1.2 hours.
- the contents of the polymerization tank were continuously extracted so that the liquid level in the polymerization tank was constant.
- methanol was supplied at 2 L / hr to the contents extracted from the second polymerization tank to deactivate the polymerization catalyst.
- hexane and unreacted monomers in the contents were removed by a solvent separator and dried to obtain a polymer.
- Example 2 the same secondary antioxidant, heat-resistant stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles. Thereafter, using a single-screw extruder manufactured by Placo Co., Ltd., the mixture was granulated at the same set temperature and resin extrusion amount as in Example 6 to obtain a measurement sample. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-3 and Tables 6-8. In a polarizing microscope observation, there is no continuous crystal structure exceeding ⁇ . As can be seen from the results of the 80 ° C tensile fatigue measurement shown in Fig. 33, this sample has higher fatigue strength than the sample used in the comparative example.
- the polymerization temperature is 85 ° C and the reaction pressure is 85 ° C.
- Polymerization was performed under the conditions of 7.9 kg / cm2G and an average residence time of 2.5 hours.
- Unreacted ethylene and hydrogen are substantially removed from the contents continuously withdrawn from the first polymerization tank by a flash drum maintained at an internal pressure of 0.30 kgZcm 2 G and 60 ° C.
- the content was continuously supplied to a second polymerization tank together with 35 liter / hr of hexane, 4.0 kg / hr of ethylene, 2.0 N-liter / hr of hydrogen, and 80 g / hr of 1-hexene, and the polymerization temperature was increased. Polymerization was continued under the conditions of 80 ° C, a reaction pressure of 2.5 kgZcm 2 G, and an average residence time of l.lhr.
- the contents of the polymerization tank were continuously extracted so that the liquid level in the polymerization tank was constant.
- methanol was supplied at 2 L / hr to the contents extracted from the second polymerization tank to deactivate the polymerization catalyst.
- hexane and unreacted monomers in the contents were removed by a solvent separator and dried to obtain a polymer.
- Example 2 the same secondary antioxidant, heat-resistant stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles. Thereafter, using a single-screw extruder manufactured by Placo Co., Ltd., the mixture was granulated at the same set temperature and resin extrusion amount as in Example 6 to obtain a measurement sample. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. In a polarizing microscope observation, there is no continuous crystal structure exceeding ⁇ . As can be seen from the results of the 80 ° C tensile fatigue measurement shown in FIG. 33, this sample has higher fatigue strength than the sample of the comparative example.
- Unreacted ethylene and hydrogen are substantially removed from the contents continuously withdrawn from the first polymerization tank by a flash drum maintained at an internal pressure of 0.30 kg / cm 2 G and 60 ° C.
- the content was continuously supplied to the second polymerization tank together with hexane 35 liter / hr, ethylene 7.0 kg / hr, hydrogen 3.0 N-liter / hr, 1-hexene 100 gZhr, and the polymerization temperature was 80 ° C. C, polymerization was continued under the conditions of a reaction pressure of 3.8 kg / cm 2 G and an average residence time of l.lhr.
- the contents of the polymerization tank were continuously extracted so that the liquid level in the polymerization tank was constant.
- methanol was supplied at 2 L / hr to the contents extracted from the second polymerization tank to deactivate the polymerization catalyst.
- hexane and unreacted monomers in the contents were removed by a solvent separator and dried to obtain a polymer.
- Example 2 the same secondary antioxidant, heat-resistant stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles. Thereafter, using a single-screw extruder manufactured by Placo Co., Ltd., the mixture was granulated at the same set temperature and resin extrusion amount as in Example 6 to obtain a measurement sample. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. In a polarizing microscope observation, there is no continuous crystal structure exceeding ⁇ . As can be seen from the results of the 80 ° C tensile fatigue measurement shown in FIG. 33, this sample has higher fatigue strength than the sample of the comparative example. In addition, as shown in Fig. 34, even at 23 ° C tensile fatigue measurement, The strength is higher than the sample of the comparative example.
- the autoclave was charged with 0.25 ml (0.25 mmol) of triisobutylaluminum and 1.0 ml of 1-hexene at a concentration of ImolZ liter, and pressurized to 8.0 kg / cm 2 G with ethylene / hydrogen mixed gas containing 0.10 vol% of hydrogen. Polymerization was started again at 80 ° C. During the polymerization, a mixed gas of ethylene and hydrogen was added so as to maintain 8.0 kg / cm 2 G, and polymerization was performed for 15.75 minutes. After the polymerization was completed, the pressure was released, and the catalyst was deactivated by adding methanol. Then, the polymer was filtered, washed, and dried at 80 ° C under vacuum for 12 hours. The obtained polymer weighed 102.50 g.
- Example 2 The same secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles. Then, using Toyo Seiki Labo Plastmill, melt-kneading at the same set temperature, resin charge amount, number of revolutions, and melting time as used in Example 1, then take out and form a sheet with a cooling press at 20 ° C. This was cut into a suitable size to obtain a sample for measurement. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. In a polarizing microscope observation, there is no continuous crystal structure exceeding ⁇ . Superior in rigidity and ESCR property as compared with the comparative example.
- the content was continuously supplied to a second polymerization tank together with hexane 35 liter / hr, ethylene 5.0 kgZhr, hydrogen 1.5 N-litrezo'hr ⁇ 1-hexene 55 g / hr, and a polymerization temperature of 70 ° C. C.
- the polymerization was continued under the condition that the reaction pressure was 0.5 kg and the average residence time was 1.21-ir.
- the contents of the polymerization tank were continuously extracted so that the liquid level in the polymerization tank was constant.
- methanol was supplied at 2 liter hr to the contents extracted from the second polymerization tank to deactivate the polymerization catalyst. . Thereafter, hexane and unreacted monomers in the contents were removed by a solvent separator and dried to obtain a polymer.
- Example 2 the same secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles in the same parts. Thereafter, using a Bravo twin-screw extruder, the mixture was granulated at a set temperature of 190 ° C at a resin extrusion rate of 20 gZmin and 100 rpm to obtain a sample for measurement. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-5. In a polarizing microscope observation, there is no continuous crystal structure exceeding ⁇ . Superior in rigidity and ESCR property as compared with the comparative example. It was also found that the physical properties of the molded bottle were superior to those of the comparative example. '
- the content was continuously supplied to the second polymerization tank together with 43 liters / hr of hexane, 3.8 kg / hr of ethylene, 14.0 N-liter / hr of hydrogen, and 20 g / hr of 1-hexene. Temperature 75. C, the reaction pressure was 4.2 kgZcm 2 G, and the polymerization was continued under the conditions of an average residence time of l.Ohr. In the second polymerization tank, the contents of the polymerization tank were continuously extracted so that the liquid level in the polymerization tank was constant.
- Tables 1-4 The results are shown in Tables 1-4.
- Table 5 shows the results of measuring the physical properties by bottle molding using the sample. According to observation with a polarizing microscope, there is no continuous crystal structure exceeding ⁇ .
- the bottle molded body is superior in rigidity as compared with the comparative example, and superior in moldability as compared with the other examples.
- the solid catalyst component ( ⁇ ) obtained in Synthesis Example 5 was converted to Zr atoms at 0.13 mmol, hr, triethylaluminum was 20 mmol / hr, ethylene was 5.0 kg / hr.
- hr While continuously supplying hydrogen at 67 N-liter / hr and continuously extracting the contents of the polymerization tank so that the liquid level in the polymerization tank is constant, the polymerization temperature is 85 ° C and the reaction pressure is 7.4 kg. The polymerization was carried out under the conditions of / cm 2 G and an average residence time of 2.7 hours.
- Unreacted ethylene and hydrogen are substantially removed from the contents continuously withdrawn from the first polymerization tank by a flash drum maintained at an internal pressure of O OkgZcn ⁇ G 60 ° C.
- the content was continuously supplied to the second polymerization tank together with hexane 43 liters / hr, ethylene 3.9 kg / hr, hydrogen 10.0 N-liter Zhr, l-hexene 110 g / hr, and the polymerization temperature was 75 Polymerization was continued under the conditions of ° C ° reaction pressure 4.5 kg / cm 2 G and average residence time l.lhr. In the second polymerization tank, the contents of the polymerization tank were continuously extracted so that the liquid level in the polymerization tank was constant.
- Example 2 the same secondary antioxidant, heat stabilizer, and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles. Thereafter, using a single screw extruder manufactured by Placo Co., Ltd., the mixture was granulated at the same set temperature and resin extrusion amount as in Example 6 to obtain a measurement sample. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-3 and 6-8. In a polarizing microscope observation, there is no continuous crystal structure exceeding lOpn. As can be seen from the results of the 80 ° C tensile fatigue measurement shown in FIG. 33, this sample has higher fatigue strength than the comparative example. Also, as shown in FIG. 34, the strength was higher in the 23 ° C tensile fatigue measurement than in the other comparative examples.
- Unreacted ethylene and hydrogen are substantially removed from the contents continuously withdrawn from the first polymerization tank by a flash drum maintained at an internal pressure of 0.2 kg / cm 2 G and 65 ° C.
- the content was continuously supplied to the second polymerization tank together with 35 liter / hr of hexane, 4.0 kg / hr of ethylene, 50 ng of hydrogen / ON-liter / hr, and 50 g of 1-hexene at a polymerization temperature.
- Polymerization was carried out continuously at Bow I under the conditions of 80 ° C, a reaction pressure of 2.8 kg / cm 2 G, and an average residence time of 1.2 hr.
- the contents of the polymerization tank were continuously extracted so that the liquid level in the polymerization tank was constant.
- methanol was supplied at 2 L / hr to the contents extracted from the second polymerization tank to deactivate the polymerization catalyst.
- hexane and unreacted monomers in the contents were removed by a solvent separation device and dried to obtain a polymer.
- Example 2 the same secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the particulate ethylene polymer in the same parts by weight. Thereafter, using a Bravo twin screw extruder BT-30, the same set temperature, resin extrusion rate and rotation as in Example 11 were used. The sample was granulated under the following conditions to obtain a measurement sample. In a polarizing microscope observation with a 100-fold field of view, there is no continuous crystal structure exceeding ⁇ . A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 4 '. Table 5 shows the results of measuring the physical properties by bottle molding using the sample.
- Example 1 The same secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles obtained in Example 4 in the same amount. Thereafter, using a twin-screw extruder # -30 manufactured by Bravo, granulation was performed under the same conditions of the set temperature, resin extrusion rate, and rotation speed as in Example 11, to obtain a measurement sample. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. In a polarizing microscope observation, there is no continuous crystal structure exceeding ⁇ . A continuous crystal structure exceeding ⁇ ⁇ ⁇ did not exist in a polarizing microscope observation with a 100-fold visual field. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 5. Table 5 shows the results of measuring the physical properties by bottle molding using the sample.
- Example 2 The same secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles. After working hard, Toyo Seiki Lab Plastomi After melt-kneading under the same set temperature, resin charge amount, rotation speed, and melting time conditions as used in Example 1, take out and form a sheet with a cooling press set at 20 ° C. Samples for measurement were obtained by cutting to size. In a polarizing microscope observation, there is no continuous crystal structure exceeding ⁇ . Soluble in 140 ° C decane. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. Superior in rigidity and ESCR compared to the comparative example.
- Example 1 The same secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles obtained in Example 14 in the same parts by weight. Then, use a Toyo Seiki Labo Plastomill, melt-knead the same temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, then take out and cool at 20 ° C. A sheet was formed by pressing, and this was cut into an appropriate size to obtain a measurement sample. According to observation with a polarizing microscope, there is no continuous crystal structure exceeding ⁇ . Soluble in 140 ° C decane. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. Excellent rigidity and ESCR properties compared to the comparative example.
- Example 2 the same secondary antioxidant, heat-resistant stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles. Thereafter, using a Toyo Seiki Labo Plastomill, melt-kneading at the same set temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, take out and sheet with a cooling press set at 20 ° C. This was cut into a suitable size, and used as a measurement sample. In a polarizing microscope observation, there was no continuous crystal structure exceeding ⁇ ⁇ . Soluble in 140 ° C decane. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. Higher rigidity than the comparative example.
- Example 2 The same secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles obtained in Example 4 in the same amount. Thereafter, using a 20 mmcp single screw extruder manufactured by Thermoplastics Co., Ltd., the mixture was granulated at a set temperature of 190 ° C. with a resin extrusion rate of 60 gZmin and 100 rpm to obtain a sample for measurement. In a polarizing microscope observation, there is no continuous crystal structure exceeding ⁇ . Soluble in 140 ° C decane. Further, a press sheet was prepared using the sample, and physical properties were measured. The results are shown in Tables 1-4. Since the smoothness is lower than that of Example 4, the ESCR property is also low.
- a press sheet was prepared using Novatec HD HB332R product pellets manufactured by Japan Polyethylene Corporation, and the physical properties were measured. The results are shown in Tables 1-4. It is inferior in rigidity and ESCR property as compared with the embodiment.
- Example 2 The same secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles obtained in Example 3 in the same amount. Thereafter, a 20 mm ⁇ p single screw extruder manufactured by Thermoplastics Co., Ltd. was used and granulated at the same set temperature, resin extrusion rate, and rotation speed as in Comparative Example 1 to obtain a sample for measurement. In a polarizing microscope observation, there was no continuous crystal structure exceeding ⁇ ⁇ . Soluble in 140 ° C decane. In addition, the sample Then, a press sheet was prepared and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. Low smoothness compared to Example 3. The results of the 80 ° C tensile fatigue measurement shown in FIG. 33 indicate that the fatigue strength is lower than the comparative example. The fracture surface of the sample after the measurement of tensile fatigue broke with almost no elongation.
- the reactor was purged with nitrogen, the prepolymerized catalyst was filtered under a nitrogen atmosphere with a glass filter sufficiently purged with nitrogen, washed three times with purified hexane, and suspended in about 100 ml of purified decane. All the liquid was transferred to a catalyst bottle to obtain a solid catalyst component ( ⁇ ).
- Example 2 The same secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles. After a while, Toyo Seiki Lab Plastomi After melt-kneading at the same set temperature, resin charge amount, rotation speed, and melting time conditions as used in Example 1, take out and form a sheet with a cooling press set at 20 ° C. A sample for measurement was obtained by cutting into pieces. In a polarizing microscope observation, there is no continuous crystal structure exceeding ⁇ . Soluble in 140 ° C decane. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6.
- this polymer has a lower fatigue strength than the polymer of Example 2).
- the fracture surface of the sample after the measurement of tensile fatigue broke with almost no elongation.
- Example 2 The same secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles. After squeezing, using a Toyo Seiki Labo Plastmill, melt-kneading at the same set temperature, resin charge amount, rotation speed, and melting time conditions as used in Example 1, take out and cool with a cooling press set at 20 ° C. The sheet was cut into an appropriate size, and used as a sample for measurement. In a polarizing microscope observation, there is no continuous crystal structure exceeding lOpm. Soluble in 140 ° C decane. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. No. 33 As is evident from the 80 ° C tensile fatigue measurement shown in the figure, this sample has higher fatigue strength than the sample described in the comparative example. The fracture surface of the sample after the tensile fatigue measurement was fractured with almost no elongation.
- the polymer was separated from hexane by filtration, washed with excess hexane, and dried for 3 hours. The obtained polymer weighed 102.5 kg.
- the polymer was separated from hexane by filtration, washed with excess hexane, and dried for 3 hours.
- the obtained polymer was 99.5 kg.
- Example 23 After thoroughly drying and adding 1200 liters of hexane to a nitrogen-purged polymerization reactor, introducing 650 mmol of triisobutylaluminum, pressurizing and depressurizing with ethylene three times to remove nitrogen in the polymerization reactor Repeated.
- the temperature in the polymerization vessel was increased to 70 ° C.
- the pressure was increased to 0.50 MPa with ethylene, and the pressure was further increased with hydrogen so that the hydrogen concentration in the gas phase became 29 mol%.
- the solid catalyst component ( ⁇ ) obtained in Synthesis Example 5 was converted into Zr atoms and charged with l.bmmol, and at the same time, ethylene was fed at a rate of 32 Nm 3 / hr and hydrogen was fed at a rate of 0.1 Nm 3 / hr.
- ethylene was fed at a rate of 32 Nm 3 / hr
- hydrogen was fed at a rate of 0.1 Nm 3 / hr.
- the polymer was separated from hexane by filtration, washed with excess hexane, and dried for 3 hours. The obtained polymer weighed 91.0 kg.
- Example 2 the same secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles. Thereafter, using a Toyo Seiki Labo Plastomill, melt-kneading at the same set temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, take out and sheet with a cooling press set at 20 ° C. This was cut into a suitable size, and used as a measurement sample. In polarized light microscopy observations, there was no continuous crystal structure exceeding ⁇ . It was soluble in 140 ° C decane. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-3 and Tables 7-8. As shown in the 23 ° C tensile fatigue measurement results shown in Fig. 34, this sample was used in the comparative example. Strength is higher than that of the sample.
- a 200-liter autoclave equipped with a stirrer was charged with 86.5 liters of heptane, 90 mmol of triisobutylaluminum, and 9 g of the solid catalyst component ( ⁇ ) prepared in Synthesis Example 7.
- the polymerization was carried out while maintaining the internal temperature at 80 ° C, charging ethylene and hydrogen, and maintaining the internal pressure at 0.6 MPaZG.
- the amount of ethylene charged was 13.7 kg.
- Example 2 the same secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as used in Example 1 were mixed with 100 parts by weight of the polymer particles.
- a sheet was formed by pressing, and this was cut into an appropriate size to obtain a measurement sample. In a polarizing microscope observation, there was no continuous crystal structure exceeding ⁇ . Soluble in 140 ° C decane.
- a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-3 and Tables 7-8. As shown in the results of the 23 ° C bow I tension fatigue measurement shown in FIG. 34, this sample is stronger than the sample used in the comparative example. table 1
- Example 1 69 393,000 1.9 10
- Example 1 20,800 2.1 61 381,000 2.1 12
- Example 1 2 35,600 2.2 69 287,000 2.2 10
- Example 1 3 26,300 2.1 60 461,000 2.1 11
- Example 1 5 18,600 2.3 71 539,000 2.3 14
- Example 1 7 18,600 2.3 71 539,000 2.3 15
- Comparative example 8 49,800 3.1 82 352,000 2.9-Comparative example 27,600 2.0 58 416,000 1.9 110 Comparative example 1 0 24,000 2.4 47 301,000 2.4 11
- Example 20 25,300 2.5 57 450,000 2.1 10
- Example 21 10,700 2.2 57 564,000 3.0 12
- Example 22 11,900 2.1 60 53
- the ethylene-based polymer of the present invention provides a molded article having excellent moldability and excellent mechanical strength and excellent appearance.
- excellent properties are provided.
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Abstract
Description
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EP04711698A EP1595897B1 (en) | 2003-02-17 | 2004-02-17 | Ethylene polymer and application thereof to moldings |
US10/542,756 US7700708B2 (en) | 2003-02-17 | 2004-02-17 | Ethylene polymer and application thereof to moldings |
DE602004030660T DE602004030660D1 (de) | 2003-02-17 | 2004-02-17 | Ethylenpolymer und dessen anwendung auf formkörper |
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EP (1) | EP1595897B1 (ja) |
KR (1) | KR100704261B1 (ja) |
CN (1) | CN100344657C (ja) |
DE (1) | DE602004030660D1 (ja) |
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- 2004-02-17 TW TW093103731A patent/TWI263646B/zh not_active IP Right Cessation
- 2004-02-17 EP EP04711698A patent/EP1595897B1/en not_active Expired - Lifetime
- 2004-02-17 DE DE602004030660T patent/DE602004030660D1/de not_active Expired - Lifetime
- 2004-02-17 KR KR1020057014629A patent/KR100704261B1/ko active IP Right Grant
- 2004-02-17 CN CNB2004800043872A patent/CN100344657C/zh not_active Expired - Lifetime
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Cited By (10)
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US8129489B2 (en) * | 2004-08-16 | 2012-03-06 | Mitsui Chemicals, Inc. | Ethylene polymer and use thereof |
US7605208B2 (en) | 2005-10-31 | 2009-10-20 | Mitsui Chemicals, Inc. | Process for producing thermoplastic resin composition |
WO2007105483A1 (ja) | 2006-03-10 | 2007-09-20 | Mitsui Chemicals, Inc. | インフレーション成形による成形体の製造方法 |
WO2007111249A1 (ja) | 2006-03-27 | 2007-10-04 | Mitsui Chemicals, Inc. | Tダイ成形による成形体の製造方法 |
WO2007122906A1 (ja) | 2006-03-29 | 2007-11-01 | Mitsui Chemicals, Inc. | ブロー成形による成形体の製造方法 |
WO2007114009A1 (ja) | 2006-03-30 | 2007-10-11 | Mitsui Chemicals, Inc. | 射出成形による成形体の製造方法 |
WO2008087945A1 (ja) | 2007-01-16 | 2008-07-24 | Prime Polymer Co., Ltd. | 中空成形体用エチレン系樹脂組成物及びそれからなる中空成形体 |
US9000116B2 (en) | 2007-01-16 | 2015-04-07 | Prime Polymer Co., Ltd. | Blow molding ethylene resin composition and blow molded article therefrom |
JP7483464B2 (ja) | 2020-03-31 | 2024-05-15 | 三井化学株式会社 | エチレン系重合体の製造方法 |
JP7483465B2 (ja) | 2020-03-31 | 2024-05-15 | 三井化学株式会社 | エチレン系重合体の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN1751072A (zh) | 2006-03-22 |
US20060189775A1 (en) | 2006-08-24 |
EP1595897A4 (en) | 2008-01-16 |
EP1595897B1 (en) | 2010-12-22 |
KR20050106003A (ko) | 2005-11-08 |
US7700708B2 (en) | 2010-04-20 |
KR100704261B1 (ko) | 2007-04-06 |
TW200424218A (en) | 2004-11-16 |
CN100344657C (zh) | 2007-10-24 |
DE602004030660D1 (de) | 2011-02-03 |
TWI263646B (en) | 2006-10-11 |
EP1595897A1 (en) | 2005-11-16 |
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